EP1593000B1 - Afficheur electrochrome - Google Patents
Afficheur electrochrome Download PDFInfo
- Publication number
- EP1593000B1 EP1593000B1 EP04706771A EP04706771A EP1593000B1 EP 1593000 B1 EP1593000 B1 EP 1593000B1 EP 04706771 A EP04706771 A EP 04706771A EP 04706771 A EP04706771 A EP 04706771A EP 1593000 B1 EP1593000 B1 EP 1593000B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrochromic
- doped
- working electrode
- layer
- tio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000012777 electrically insulating material Substances 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 37
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 33
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 9
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 229910003437 indium oxide Inorganic materials 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000003566 sealing material Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002322 conducting polymer Substances 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 4
- 239000011244 liquid electrolyte Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 3
- 229910005264 GaInO3 Inorganic materials 0.000 claims description 2
- 229910017902 MgIn2O4 Inorganic materials 0.000 claims description 2
- 229910007694 ZnSnO3 Inorganic materials 0.000 claims description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 239000011810 insulating material Substances 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000012780 transparent material Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 2
- 229910004158 TaO Inorganic materials 0.000 claims 1
- BFRGSJVXBIWTCF-UHFFFAOYSA-N niobium monoxide Inorganic materials [Nb]=O BFRGSJVXBIWTCF-UHFFFAOYSA-N 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- -1 for example Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- HSTRVBYSLWZHSR-UHFFFAOYSA-O 2,5-dimethyl-3-propyl-1H-imidazol-3-ium Chemical compound CCC[NH+]1C=C(C)N=C1C HSTRVBYSLWZHSR-UHFFFAOYSA-O 0.000 description 1
- PZYQWVWYKLGFIL-UHFFFAOYSA-N 2-[4-[1-(2-phosphonoethyl)pyridin-1-ium-4-yl]pyridin-1-ium-1-yl]ethylphosphonic acid;dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](CCP(O)(=O)O)=CC=C1C1=CC=[N+](CCP(O)(O)=O)C=C1 PZYQWVWYKLGFIL-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- 244000304337 Cuminum cyminum Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- JROGBPMEKVAPEH-GXGBFOEMSA-N emetine dihydrochloride Chemical compound Cl.Cl.N1CCC2=CC(OC)=C(OC)C=C2[C@H]1C[C@H]1C[C@H]2C3=CC(OC)=C(OC)C=C3CCN2C[C@@H]1CC JROGBPMEKVAPEH-GXGBFOEMSA-N 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/155—Electrodes
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1503—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/1533—Constructional details structural features not otherwise provided for
- G02F2001/1536—Constructional details structural features not otherwise provided for additional, e.g. protective, layer inside the cell
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/155—Electrodes
- G02F2001/1552—Inner electrode, e.g. the electrochromic layer being sandwiched between the inner electrode and the support substrate
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/155—Electrodes
- G02F2001/1555—Counter electrode
Definitions
- This invention relates to an electrochromic device.
- it relates to an electrochromic device in which the components are built up on a single substrate which need not be transparent.
- Such devices are often referred to as monolithic devices.
- Electrochromic systems are based on colour changes that are caused by electrochemical reactions in various types of metal oxides or organic or inorganic compounds. Electrochromic devices are well known in the art.
- a typical electrochromic device architecture is the sandwich type architecture, which in its simplest form consists of two glass substrates on the outside and between them a counter and working electrode, an electrochromic material and an electrolyte which allows for the passage of ions.
- Such a device is disclosed in e.g. EP-A-1244168; Bach, U. et al, Adv. Mater. 2002, 14, No. 11, June 5 and Cummins et al, J. Phys. Chem B 2000, 104, 11449-11459.
- the document EP-1 244 168 A discloses the features labeled (a) to (c) in claim 1 in combination.
- One disadvantage of the sandwich type-architecture is that the electrochromic layer is typically viewed through a transparent substrate, such as glass which is covered with a transparent conducting layer. Transmission values for such conducting transparent substrates, e.g. glass or plastic coated with an electrically conducting material, are typically in the region of 70 - 90%. In reflective display applications, the light must pass through this layer twice when being diffusely reflected. This results in transmission losses of 19-51%, thereby limiting the maximum diffuse reflectance in the "off" state of the device to 49-81%.
- WO-A-97/16838 discloses a monolithic device for solar cell applications.
- This device has a "classic" monolithic architecture, i.e. the working electrode layer is deposited directly onto a transparent conducting supporting substrate and is therefore the bottom layer of the device.
- WO-A-01/97237 also discloses a monolithic device having a "classic" monolithic architecture where the working electrode (photoelectrode) is deposited directly onto a transparent conducting supporting substrate.
- a major disadvantage of the existing monolithic devices is that they only allow deposition of electrochromic coatings onto transparent substrates, thus limiting their applications. Furthermore, pixels must be viewed through at least two layers of material, thereby adversely affecting the reflectance of the conventional devices.
- an electrochromic device comprising a single supporting substrate on which are disposed:
- electrochromic material is intended to refer to a material which changes colour on the application of an electrical potential thereto.
- substantially all of the major surface of the electrochromic material may form a portion of the external surface of the device.
- the working electrode preferably has a major surface which may be electrochromic per se or may bear electrochromic material on at least a portion thereof.
- the electrochromic material may substantially cover the major surface of the working electrode.
- the working electrode, counter electrode and insulating layers may be substantially parallel along their length. These layers may also be substantially coextensive with one another.
- the supporting substrate may be formed from any suitable transparent or non-transparent material, such as glass or metal or a ceramic or plastics material.
- the substrate may be rendered electrically conducting by applying an electrically conducting coating to at least a portion of the internal surface thereof.
- the electrically conducting coating preferably comprises a doped metal oxide, such as, for example, tin oxide doped with fluorine or antimony, or indium oxide doped with tin, or a conducting polymer or metal.
- a doped metal oxide such as, for example, tin oxide doped with fluorine or antimony, or indium oxide doped with tin, or a conducting polymer or metal.
- the intrinsic sheet resistance of the material of the working electrode and/or the counter electrode is less than 10,000 ohms per square, the application of an electrically conducting coating to the substrate may not be required.
- the working electrode may be arranged so that at least a portion thereof is laterally offset from the counter electrode.
- the working and counter electrodes comprise an electrically conducting or semiconducting material.
- a preferred electrically conducting material of the working and/or counter electrodes comprises nanoparticles of a metal oxide selected from any of the following:
- a preferred electrically semiconducting material of the working and/or counter electrodes comprises nanoparticles of a metal oxide selected from any of the following:
- such a material may include metal or doped metal oxides.
- oxides include WO 3 , TiO 2 , antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO) and tin doped indium oxide (ITO).
- ATO antimony doped tin oxide
- FTO fluorine doped tin oxide
- ITO tin doped indium oxide
- electrochromic material is preferably selected from viologens and polymers and mixtures thereof.
- Suitable viologens are disclosed in WO-A-98/35267, WO-A-01/27690, WO-A-03/001288 and a copending PCT Application entitled “Electrochromic Compounds", filed on even date by the Applicant (NTera Limited).
- Suitable polymers include polythiophenes, polypyrroles and polyviologens.
- the electrically insulating layer is preferably transparent or light-scattering and may comprise organic or inorganic material.
- This layer may also be porous.
- Such a porous layer preferably comprises a metal oxide selected from SiO 2 , Al 2 O 3 , ZrO and MgO, or TiO 2 in the rutile form passivated with SiO 2 .
- the inventive device may additionally comprise an ion-conducting medium.
- the electrically insulating layer of the device may comprise an ion-conducting medium.
- polyethylene glycol could serve as both insulator and solid electrolyte.
- the ion-conducting medium may be present in the device as an additional layer of solid electrolyte.
- the electrically insulating layer is porous, each of the porous layers is at least partially sealed, and the ion-conducting medium comprises a liquid electrolyte which at least partially fills the pores of the electrodes and the insulating material.
- the device of the invention preferably also comprises a transparent cover or top layer at least partially exposing the electrochromic material and a sealing material sealing the cover to the electrochromic device.
- the sealing material seals the cover to the supporting substrate.
- the liquid electrolyte when present, preferably comprises at least one electrochemically inert salt optionally in molten form or in solution in a solvent.
- suitable salts include hexafluorophosphate, bis-trifluoromethanesulfonate, bis-trifluoromethylsulfonylimide, tetraalkylammonium, dialkyl-1,3-imidazolium and lithium perchlorate.
- suitable molten salts include trifluoromethanesulfonate, 1-ethyl,3-methyl imidazolium bis-trifluoromethylsulfonylimide and 1-propyldimethyl imidazolium bis-trifluoromethylsulfonylimide. Lithium perchlorate is particularly preferred.
- the solvent may be any suitable solvent and is preferably selected from acetonitrile, butyronitrile, glutaronitrile, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methyloxazolidinone, dimethyltetrahydropyrimidinone, ⁇ -butyrolactone and mixtures thereof. Lithium perchlorate in ⁇ -butyrolactone is particularly preferred.
- the device of the invention may optionally comprise an electrical current supporting layer interposed between the (semi) conducting material of the working electrode and the electrically insulating material.
- the electrical current supporting layer is formed from a porous, electrically conducting material which enables the transport of charge between the device components.
- This layer may suitably comprise indium oxide doped with tin or tin oxide doped with fluorine, or conducting polymers such as polythiophenes, polypyrroles and polyviologens.
- the device of the invention may be conveniently sealed using a suitable sealing material and a transparent cover of glass or a plastics material disposed on the external surface of the layer remote from the supporting substrate.
- the invention also provides a display comprising one or more devices according to the invention.
- a plurality of devices according to the invention may also be connected in series, forming an assembly.
- the device/assembly of the invention may be used in an active matrix or passive matrix or in direct drive configurations.
- Figure 1 is a cross sectional diagram of one embodiment of a monolithic device according to the invention
- Figure 2 is a cross sectional diagram of another embodiment of a monolithic device according to the invention
- Figure 3 shows a plurality of the devices of Figure 2 connected in series
- Figures 4A and 4B are photographs of a top plan view of the device of Figure 2 containing three independent electrochromic pixels.
- the device of Figure 1 comprises a supporting substrate 1, which may be glass, plastic, ceramic or other suitable material.
- the substrate 1 bears a conducting coating or layer 2 that provides contact for a display device to external electronic controls.
- This layer 2 is patterned to allow for individual contact to pixels in a display and also for individual contact to working and counter electrode layers 6 and 3, respectively.
- the counter electrode layer 3 comprises a material porous to ions and is electrically conducting. Layer 3 is physically in contact with layer 2 and electrical current can flow between these layers.
- the working and counter electrodes are separated by a porous insulating layer 4.
- Layer 4 is porous to ions and is electrically insulating.
- the layer 4 is physically deposited on top of the counter electrode layer 3 and provides insulation for subsequent layers which must not be in contact with layer 3.
- An ion porous, electrically conducting layer 5 is physically deposited on layer 4 and is in electrical contact with layer 2.
- Layer 5 provides efficient electrical charge conduction to the working electrode layer/electrochromic layer 6.
- the major surface of the layer 6, i.e. the viewing surface, is denoted by x.
- the device of Figure 2 is the same as that of Figure 1 except that the insulating layer 4 includes a via hole that allows contact between layer 2 and layer 5 such that electrical charge may be directed to the pixel.
- the electrically conducting layer 5 is physically deposited on layer 4 and is in electrical contact with layer 2 by filling in the via hole.
- Figures 4A and 4B the device is viewed through a layer of plain glass which is disposed on the external (viewing) surface of the layer 6 and sealed to the supporting substrate of the device.
- the seal of the device is visible as a black square.
- the space between the top glass plate and the substrate contains liquid electrolyte.
- Figure 4A shows all three pixels in the off-state (0 volt bias), while in Figure 4B the middle pixel was switched on by applying a negative bias of 1.5 V to the working electrode relative to its underlying counter electrode (not visible).
- the invention is illustrated in the following Example.
- a supporting substrate in the form of glass coated with tin doped indium oxide (ITO) was patterned according to standard wet-etching techniques. Using screen-printing techniques the following layers were deposited on the substrate in the following sequence:
- the binder used in each of the above steps (a)-(d) was hydroxypropyl cellulose (Klucel EXF PHARM); and the solvent was terpineol (anhydrous, Fluka).
- the electrically insulating layer (b) was prepared using the materials listed below according to the procedure described by Kay et al. in Solar Energy Materials and Solar Cells (1996), 44(1), pp 99 - 117.
- the layered structure was sintered at 450°C for 30 minutes, exposed to a solution of bis-(2-phosphonoethyl)-4,4'-bipyridinium dichloride in water, rinsed, dried and sealed using an epoxy sealing ring and a top glass cover.
- the device was backfilled with the electrolyte lithium perchlorate in gamma-butyrolactone.
- the Sb-doped SnO 2 layer is used as a counter electrode, which can store or release charge and is necessary to show the electrochromic effect of the electrochromic layer.
- the rutile layer electrically insulates the doped SnO 2 layer from the electrochromic layer and provides a 'white background' for the device. Ionic movement through this layer is facilitated due to its porous structure.
- the ITO layer is used as an electrical current supporting layer. It appears opaque (nearly white). Ionic movement through this layer is facilitated due to its porous structure. Its sheet resistance is lower than 1 k ⁇ / ⁇ .
- the viologen-derivatised mesoporous TiO 2 layer is used as electrochromic layer.
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Control Of Indicators Other Than Cathode Ray Tubes (AREA)
- Gas-Insulated Switchgears (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Claims (27)
- Dispositif électrochromique comprenant un substrat de support unique (1) sur lequel sont disposées :(a) une électrode de travail (6) comprenant une couche poreuse d'une matière électriquement conductrice ou semi-conductrice, l'électrode de travail comprenant une matière qui est électrochromique en soi et/ou au moins une partie de ladite électrode de travail portant une matière électrochromique ;(b) une contre-électrode (3) comprenant une couche poreuse d'une matière électriquement conductrice ou semi-conductrice ;(c) une couche (4) d'une matière électriquement isolante qui est perméable aux ions et qui sépare les couches d'électrode de travail et de contre-électrode ; dans lequel ladite matière électrochromique a une surface principale dont au moins une partie forme au moins une partie d'une surface externe du dispositif.
- Dispositif selon la revendication 1, dans lequel essentiellement la totalité de ladite surface principale forme une partie de la surface externe du dispositif.
- Dispositif selon la revendication 1 ou 2, dans lequel ladite électrode de travail comporte une surface principale qui est électrochromique en soi.
- Dispositif selon la revendication 1 ou 2, dans lequel ladite électrode de travail comporte une surface principale dont au moins une partie porte une matière électrochromique.
- Dispositif selon la revendication 4, dans lequel ladite matière électrochromique couvre essentiellement ladite surface principale de ladite électrode de travail.
- Dispositif selon l'une quelconque des revendications précédentes, dans lequel l'électrode de travail, la contre-électrode et les couches isolantes sont essentiellement parallèles ; et/ou dans lequel l'électrode de travail, la contre-électrode et les couches isolantes s'étendent essentiellement dans le même sens les unes par rapport aux autres.
- Dispositif selon l'une quelconque des revendications 1 à 5, dans lequel au moins une partie de l'électrode de travail est décalée latéralement par rapport à la contre-électrode.
- Dispositif selon l'une quelconque des revendications précédentes, dans lequel le substrat de support est formé à partir d'une matière transparente ou non transparente.
- Dispositif selon la revendication 8, dans lequel le substrat est formé en verre ou métal ou en une matière céramique ou plastique.
- Dispositif selon la revendication 8 ou 9, dans lequel le substrat de support porte un revêtement électriquement conducteur sur au moins une partie de sa surface interne.
- Dispositif selon la revendication 10, dans lequel le revêtement électriquement conducteur comprend un oxyde métallique dopé, de préférence de l'oxyde d'étain dopé au fluor ou à l'antimoine, ou de l'oxyde d'indium dopé à l'étain, ou un polymère ou métal conducteur.
- Dispositif selon l'une quelconque des revendications 1 à 9, dans lequel la résistance de couche intrinsèque de la matière de l'électrode de travail et/ou de la contre-électrode est inférieure à 10000 ohms par carré.
- Dispositif selon l'une quelconque des revendications précédentes, dans lequel l'électrode de travail et/ou la contre-électrode comprennent une matière électriquement conductrice comprenant des nanoparticules d'un oxyde métallique sélectionné parmi les oxydes métalliques suivants :(a) SnO2 dopé au F, Cl, Sb, P, As ou B ;(b) ZnO dopé à l'Al, In, Ga, B, F, Si, Ge, Ti, Zr ou Hf ;(c) In2O3 dopé au Sn ;(d) CdO;(e) ZnSnO3, Zn2h2O5, In4Sn3O12, GaInO3 ou MgIn2O4 ;(f) Fe2O3 dopé au Sb ;(g) Systèmes TiO2/WO3 ou TiO2/MoO3 ; et(h) Systèmes Fe2O3/Sb ou SnO2/Sb ;de préférence du SnO2 dopé au Sb.
- Dispositif selon l'une quelconque des revendications 1 à 13, dans lequel l'électrode de travail et/ou la contre-électrode comprennent une matière électriquement semi-conductrice comprenant des nanoparticules d'un oxyde métallique sélectionné parmi les oxydes métalliques suivants : TiO2, ZrO2, HfO2, CrO3, MoO3, WO3, VO, NbO, SnO2, TaO, AgO, ZnO, SrO, FeO, Fe2O3 ou NiO, ou un pérovskite de ceux-ci, de préférence le TiO2, WO3, MoO3, ZnO ou SnO2.
- Dispositif selon la revendication 3 ou n'importe quelle revendication dépendant de celle-ci, dans lequel la matière électrochromique de l'électrode de travail est un oxyde métallique sélectionné parmi le WO3 et le TiO2 ou un oxyde métallique dopé sélectionné parmi l'oxyde d'étain dopé à l'antimoine ou au fluor et l'oxyde d'indium dopé à l'étain.
- Dispositif selon la revendication 4 ou n'importe quelle revendication dépendant de celle-ci, dans lequel la matière électrochromique est sélectionnée parmi les viologènes et polymères et mélanges de ceux-ci.
- Dispositif selon l'une quelconque des revendications précédentes, comprenant en outre un milieu de conduction ionique.
- Dispositif selon l'une quelconque des revendications précédentes, dans lequel la couche électriquement isolante comprend un milieu de conduction ionique.
- Dispositif selon l'une quelconque des revendications 1 à 17, dans lequel la matière électriquement isolante est poreuse et chacune des couches poreuses est au moins partiellement scellée, et le milieu de conduction ionique comprend un électrolyte liquide qui remplit au moins partiellement les pores des électrodes et la matière isolante.
- Dispositif selon l'une quelconque des revendications précédentes, comprenant en outre un couvercle transparent qui expose au moins partiellement ladite matière électrochromique et une matière d'étanchéité qui scelle le couvercle sur ledit dispositif électrochromique.
- Dispositif selon la revendication 20, dans lequel ladite matière d'étanchéité scelle ledit couvercle sur ledit substrat de support.
- Dispositif selon l'une quelconque des revendications 19 à 21, dans lequel la matière électriquement isolante comprend un oxyde métallique sélectionné parmi les SiO2, Al2O3, ZrO et MgO, ou TiO2 sous la forme rutile passivée au SiO2.
- Dispositif selon l'une quelconque des revendications précédentes, comprenant en outre une couche de support de courant électrique interposée entre l'électrode de travail et les couches électriquement isolantes.
- Dispositif selon la revendication 23, dans lequel la couche de support de courant électrique comprend de l'oxyde d'indium dopé à l'étain ou de l'oxyde d'étain dopé au fluor, ou un polymère conducteur sélectionné parmi les polythiophènes, les polypyrroles et les polyviologènes.
- Afficheur comprenant un ou plusieurs dispositifs selon l'une quelconque des revendications précédentes.
- Afficheur selon la revendication 25, comprenant une pluralité de dispositifs connectés en série.
- Utilisation d'un dispositif selon l'une quelconque des revendications 1 à 24 dans une matrice active ou une matrice passive ou en configurations de commande directe.
Priority Applications (2)
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EP04706771A EP1593000B1 (fr) | 2003-01-31 | 2004-01-30 | Afficheur electrochrome |
EP06014423A EP1708016B1 (fr) | 2003-01-31 | 2004-01-30 | Dispositif d'affichage électrochromique et procédé pour sa production |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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EP03394011 | 2003-01-31 | ||
EP03394011 | 2003-01-31 | ||
EP04706771A EP1593000B1 (fr) | 2003-01-31 | 2004-01-30 | Afficheur electrochrome |
PCT/IE2004/000014 WO2004068231A1 (fr) | 2003-01-31 | 2004-01-30 | Afficheur electrochrome |
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EP06014423A Division EP1708016B1 (fr) | 2003-01-31 | 2004-01-30 | Dispositif d'affichage électrochromique et procédé pour sa production |
Publications (2)
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EP1593000A1 EP1593000A1 (fr) | 2005-11-09 |
EP1593000B1 true EP1593000B1 (fr) | 2006-07-12 |
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EP06014423A Expired - Lifetime EP1708016B1 (fr) | 2003-01-31 | 2004-01-30 | Dispositif d'affichage électrochromique et procédé pour sa production |
EP04706771A Expired - Lifetime EP1593000B1 (fr) | 2003-01-31 | 2004-01-30 | Afficheur electrochrome |
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EP06014423A Expired - Lifetime EP1708016B1 (fr) | 2003-01-31 | 2004-01-30 | Dispositif d'affichage électrochromique et procédé pour sa production |
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US (1) | US7460289B2 (fr) |
EP (2) | EP1708016B1 (fr) |
JP (1) | JP4589915B2 (fr) |
KR (1) | KR100980796B1 (fr) |
CN (1) | CN100462830C (fr) |
AT (2) | ATE426187T1 (fr) |
AU (1) | AU2004208241B2 (fr) |
CA (1) | CA2509771A1 (fr) |
DE (2) | DE602004020114D1 (fr) |
DK (1) | DK1593000T3 (fr) |
HK (1) | HK1085274A1 (fr) |
TW (1) | TW200417280A (fr) |
WO (1) | WO2004068231A1 (fr) |
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DE19622600C2 (de) * | 1996-06-05 | 2001-08-02 | Fraunhofer Ges Forschung | Elektrochrome Einheit |
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EP1154311A4 (fr) * | 1999-02-18 | 2007-03-28 | Nippon Mitsubishi Oil Corp | Element electrochromique |
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-
2004
- 2004-01-30 US US10/543,527 patent/US7460289B2/en not_active Expired - Fee Related
- 2004-01-30 DE DE602004020114T patent/DE602004020114D1/de not_active Expired - Lifetime
- 2004-01-30 DE DE602004001508T patent/DE602004001508T2/de not_active Expired - Lifetime
- 2004-01-30 AT AT06014423T patent/ATE426187T1/de active
- 2004-01-30 KR KR1020057013562A patent/KR100980796B1/ko not_active IP Right Cessation
- 2004-01-30 WO PCT/IE2004/000014 patent/WO2004068231A1/fr active IP Right Grant
- 2004-01-30 EP EP06014423A patent/EP1708016B1/fr not_active Expired - Lifetime
- 2004-01-30 AU AU2004208241A patent/AU2004208241B2/en not_active Ceased
- 2004-01-30 CN CNB2004800023031A patent/CN100462830C/zh not_active Expired - Fee Related
- 2004-01-30 TW TW093102165A patent/TW200417280A/zh unknown
- 2004-01-30 JP JP2006502614A patent/JP4589915B2/ja not_active Expired - Fee Related
- 2004-01-30 EP EP04706771A patent/EP1593000B1/fr not_active Expired - Lifetime
- 2004-01-30 CA CA002509771A patent/CA2509771A1/fr not_active Abandoned
- 2004-01-30 AT AT04706771T patent/ATE333108T1/de active
- 2004-01-30 DK DK04706771T patent/DK1593000T3/da active
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2006
- 2006-05-03 HK HK06105223A patent/HK1085274A1/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
AU2004208241A1 (en) | 2004-08-12 |
AU2004208241B2 (en) | 2009-06-11 |
DE602004001508D1 (de) | 2006-08-24 |
US20060132885A1 (en) | 2006-06-22 |
JP2006520481A (ja) | 2006-09-07 |
JP4589915B2 (ja) | 2010-12-01 |
DE602004020114D1 (de) | 2009-04-30 |
HK1085274A1 (en) | 2006-08-18 |
US7460289B2 (en) | 2008-12-02 |
CA2509771A1 (fr) | 2004-08-12 |
EP1708016A2 (fr) | 2006-10-04 |
WO2004068231A1 (fr) | 2004-08-12 |
DE602004001508T2 (de) | 2007-02-15 |
ATE333108T1 (de) | 2006-08-15 |
EP1708016B1 (fr) | 2009-03-18 |
ATE426187T1 (de) | 2009-04-15 |
EP1593000A1 (fr) | 2005-11-09 |
CN1739057A (zh) | 2006-02-22 |
EP1708016A3 (fr) | 2007-10-31 |
KR20050105178A (ko) | 2005-11-03 |
DK1593000T3 (da) | 2006-10-30 |
KR100980796B1 (ko) | 2010-09-10 |
CN100462830C (zh) | 2009-02-18 |
TW200417280A (en) | 2004-09-01 |
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